Silver halide photographic emulsion

ABSTRACT

A silver halide photographic emulsion having an improved initial speed of development, especially in an infectious development process, and capable of producing a picture image with high edge gradient, which contains as the silver halide at least 40 mol % of silver chloride, with the silver halide having an average particle size of not more than 0.8 micron, and containing as a combination of the following compounds: 1. A POLYALKYLENE OXIDE COMPOUND AND 2. AN ORGANIC COMPOUND HAVING AT LEAST ONE HYDROXYL GROUP AND AT LEAST ONE AMINO GROUP CONSISTING OF A TERTIARY NITROGEN ATOM.

United States Patent Shiba et al.

14 1 Oct. 28, 1975 3,321,312 5/1967 Bardorff et al. 96/109 3,615,528 10/1971 Huckstadt et a1 96/66.3 3,632,340 1/1972 lllingsworth 96/33 3,707,376 12/1972 Van Stappen et al. 96/107 Primary Examiner-Norman G. Torchin Assistant ExaminerEdward C. Kimlin Attorney, Agent, or FirmSughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A silver halide photographic emulsion having an improved initial speed of development, especially in an infectious development process, and capable of producing a picture image with high edge gradient, which contains as the silver halide at least 40 mol of silver chloride, with the silver halide having an average particle size of not more than 0.8 micron, and containing as a combination of the following compounds:

1. a polyalkylene oxide compound and 2. an organic compound having at least one hydroxyl group and at least one amino group consisting of a tertiary nitrogen atom.

45 Claims, 3 Drawing Figures SILVER I-IALIDE PHOTOGRAPI-IIC EMULSION BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved silver halide photographic emulsion. More particularly, the invention relates to a silver halide photographic emulsion suitably used in a lith type photosensitive material having an increased sensitivity in the initial stages of an infectious development process and having increased edge gradient of the picture image resulting therefrom.

The term edge gradient" as used herein refers to the degree or rate of the change in the optical density in relation to the vertical direction to the edge formed as a contact line between the darkened and undarkened parts of the developed photographic picture image. In general, it can be said that the higher the edge gradient, the clearer or sharper the picture image is.

2. Description of the Prior Art A photosensitive material having an increased edge gradient is advantageously used, for example, as a lith type photosensitive material used in photoprinting or phototypesetting where cross-line images are formed with the use of a glass screen or a contact screen. In this type of photosensitive material, it is known to ensure simple and easy handling, that matters such as increasing the edge gradient, enhancing the sensitivity, minimizing the granularity, and accelerating the rate of developing speed are required. In addition, when development is carried out under severe conditions, it is known to retard the fatigue of the developing liquid, i.e., to increase the tolerance, etc., to minimize the degradation of the picture quality.

In order to obtain a picture image having a high edge gradient, a lith type photosensitive material for use in phototypesetting is usually developed using an infectious development process.

The infectious development process generally comprises developing with a developer containing hydroquinone as the major developing agent together with a very minor amount of a sulfite,;'an inorganic alkali salt or an organic amine, and using a pH as high as 9.5 or higher.

Development using an infectious developer inevita bly is accompanied by the disadvantages of poor sensitivity, slow initial developing speed, non-uniformity in the picture image quality obtained after every developing procedure and poor granularity of the picture image etc., as compared with another type of developer in which a developing agent capable of imparting superadditivity has been combined with the major developing agent such as is seen in the conventionally employed metolhydroquinone type developer, metolpyrazolidone type developing agent, etc. In addition, a silver halide emulsion containing a polyoxyalkylene oxide derivative is used as a lith type photo-sensitive material to strengthen the infectious development and to suppress non-infectious developability. However, the addition of such a polyalkylene oxide derivative greatly decreases the initial developing speed. In other words, a prolonged developing time is required for such emulsions to ensure infectious development with effectively high contrast. Once the infectious developing has started, the polyoxyalkylene oxide derivative strength ens the development outstandingly while providing high contrast, but a much too long period of time for the initiation of the infectious developing is required permitting, in the meantime, gradiations of extremely low contrast and high contrast to coexist thereby aggravating foot cutting.

Moreover, spectral sensitization is often applied to lith type photosensitive materials in order to increase the sensitivity in a specific wave length region. However, most of the sensitizing dyes tend to slow down the initial speed of the infectious development with an appreciable degradation of foot cutting".

When the so-called infectious development is used for the development of a lith type photosensitive material, many more disadvantages, which seriously affect the developing performance, arise due to the presence of various additives from the silver halide emulsion and due to substances which undergo chemical change during the developing procedure, than when conventional non-infectious type developers are employed.

Additives which have been conventionally used effectively in a black-and-white non-infectious type developer, e.g., D-l6, D-l9, and D-72 (these developers and their compositions are well-known in the art) are not also always similarly effective for the infectious developer. They rather invite a decrease in the edge gradient due to the disappearance of infectious developability, generate fog and promote fatigue of the developer and like disadvantageous influences.

Accordingly, an object of the present invention is to provide a photographic emulsion in which all of the defects described hereinabove have been eliminated or reduced remarkably. More particularly, an object of the present invention is to provide a photographic emulsion which satisfies the following criteria of: (l)

' increasing the initial developing speed, (2) obtaining high sensitivity with possible a minimum developing period, (3) obtaining a high edge gradient with possible a minimum developing period, (4) retaining excellent granularity while retaining high sensitivity, (5) maintaining a high edge gradient after a high degree of development, and (6) retaining satisfactory tolerance.

Another object of this invention is to provide a method for the preparation of silver halide emulsions which satisfies to a large extent the above requirements simultaneously.

, These and other objects of the present invention will be understood by referring to the following detailed disclosure and working examples thereof.

SUMMARY OF THE INVENTION It has now been found that the above objects can be accomplished with a silver halide photographic emulsion containinga silver halide comprising at least 40 .mol of silver chloride and in which the average particle diameter of the silver halide particles is not greater than 0.8 micron and further containing therein a combination of; (1) a polyalkylene oxide compound and (2) .and an organic compound having at least one hydroxyl group and at least one amino group consisting of atertiary nitrogen atom (especially one capable of promoting infectious development).

BRIEF DESCRIPTION OF THE ACCOMPANYING I DRAWINGS FIGS; 1 and 2 are each diagrams indicating the relationship between the development period and the rela- -tive sensitivity. These figures designate the speed of the development relatively.

FIG. 3 indicates voltage-current curve (polarograph) from which the oxidation potential (E is determined. Points a and b represent the points at which the three line segments intersect, each of the lines extending through the connected middle point of the curves in the ordinate direction indicating current value.

DETAILED DESCRIPTION OF THE INVENTION In more detail, the organic compound having at least one hydroxyl group and at least one amino group with a tertiary nitrogen atom, should have a specific reducing activity against the oxidation product (i.e., semiquinone) formed during the development the main developing compound (e.g., hydroquinones).

This specific compound is an aromatic compound or a heterocyclic compound (of these two, an aromatic compound is preferred) having an oxidation potential (to be defined hereinafter) (E,,,) of from about millivolt to about 200 millivolt, preferably up to l60 millivolt, or precursors (regardless of their oxidation potential) of these compounds. Especially preferred compounds are those represented by the following general formula (1 GENERAL FORMULA l wherein A represents a bivalent aromatic or heterocyclic group (e.g., a benzene group, a naphthalene group, a pyrimidine group, a triazine group), and A can be substituted with substituent groups so as to satisfy the value of E required (e.g., alkyl (e.g., methyl, ethyl, propyl, butyl, etc.), alkoxy (e.g., methoxy, ethoxy, etc.), hydroxy, halogen (e.g., chlorine, bromine, etc.), alkoxycarbonyl (e.g., methoxy carbonyl, ethoxycarbonyl, etc.), quaternary aminoalkyl, aralkyl (e.g., benzyl, phenethyl, etc.), aryl (e.g., phenyl, etc.), etc.); R, and R each represents a group which is necessary to form a tertiary amino group with the nitrogen atom, and is preferably an alkyl group (e.g., a methyl, ethyl, butyl, hydroxyalkyl such as hydroxyethyl, aminoalkyl such as trimethyl aminoethyl group, etc.), an alkenyl group (e.g., an ally] group), an aralkyl group (e.g., a benzyl, p-hydroxyphenyl-substituted alkyl group, etc.), or an aryl group (e.g., a phenyl, hydroxyphenyl, acetoxyphenyl, alkoxycarbonyloxyphenyl group, etc.), and R and R can combine together to form a closed (saturated or unsaturated) ring; X represents either hydrogen, or a group capable of being dissociated therefrom with an inorganic or organic base (e.g., an acetyl, benzoyl and like acyl groups, an acetoxy and like acyloxy groups. The compound to which these dissociatable groups are attached is defined as a precursor" which under the development conditions releases its dissociable group with the compound behaving as if X were originally a hydrogen atom.

The compound represented by the general formula (1) usually exists in a stable state as the form of a Lewis acid-base salt with an inorganic or organic acid (e.g., hydrochloride acid, sulfuric acid, nitric acid, sulfurous acid, oxalic acid, p-methylbenzene sulfonate and sulfuric acid etc.), so that it can be employed in such a stabilized form. Especially preferred compounds of the general formula (1) above are those having the general formula (La) wherein B represents a bivalent benzene type aromatic ring group, and X, R and R each is as defined with respect to the foregoing general formula (1).

Typical compounds represented by the general formula (1) and which can be employed in this invention are exemplified by the following compounds. However, the invention is not limited to these compounds only, and other compounds which have been described in German Pat. Laid-open Specification Nos. 2,153,632; 2,153,633, 2,153,571; 2,153,572, 2,161,431 etc. can be employed.

HO- N(C2H5)HCl oral J O .HCl Ho ci-i HO N(cH,)=.Hc|

HO N(C,Hs)2.HCI

r ocH HO- N(CH,,).HC|

, i-i cit,

HO- (cznmicl The compounds shown by (l-j) and (l-k) are examples of precursor compounds.

The process of development is understood as an oxidation-reduction reaction process between the silver halide and the developing compound.

Of the above-described compounds of this invention used as an element of the emulsion of this invention, the most desirable compounds for achieving the objects of this invention have the specific oxidation potental (E as set forth previously. I

The value of the oxidation, potential (E can be readily determined by voltametry as described hereinafter.

Firstly, a Britton-Robinsons buffer solution adjusted to a pH of 11.0 is prepared by mixing 825cc of a solution of sodium hydroxide (0.20N) with 1 liter of the solution containing dissolved therein 39.2g of orthophosphoric acid, 24.0g of glacial acetic acid and 24.7g of boric acid (the solution showed a pH value of ll.O at 25C). The buffer solution thus prepared is then bubbled with nitrogen gas to completely replace the air, after which the samples to be measured are dissolved therein to prepare a l l'0 mol solution of each sample. After placing a dropping mercury electrode in this solution, a voltage-current curve is plotted at 25C using a saturated calomel electrode (SCE) as a reference electrode. The oxidation potential (E is determined from this curve by determining a half-wave potential therefrom according to the usually employed graphical method.

A series of the measured values sometimes gives rise to a deviation of approximately 100 millivolts depending upon the effect of the salt of the compound, although the compensations in the liquid-liquid contact potential, electric resistance, etc. specific to the appa ratus are occasionally carried out by suitable adjustments in the electric circuits of the tripolar type polarography apparatus. However, in case of measuring only one compound, for instance, in case of measurement with hydroquinone, the reproducibility of the value of the oxidation potential can be obtained by comparing and adjusting the measured value while taking -l 50:2 millivolt as the standard.

The term oxidation potential means the electric potential at which the sample is oxidized at the anode. The methods for the measurement of the oxidation potential are described in a variety of publications such as P. Delahay, New Instrumenlal Methods in Electrochemistry, lnterscience Publishers, 1954; l. M. Kolthoft and J. J. Lingane, Polarography, Second Edition, lnterscience Publishers, 1952; L. Meites, Polarographic Techniques, Second Edition, lnterscience Publishers, 1965,

etc.

The oxidation potential as used throughout the specification refers to the one regarding the form in which a proton has been dissociated from the organic compound, and therefore it is preferred that the measurement be carried out in a solution with a sufficiently high pH value. In this case, the measurement of the oxidation potential of the organic compound represented by the general formula (1 is desirably carried out within about one hour after the preparatiorj' of the alkaline solution, since the organic compound tends to undergo decomposition, for instance'fde'a'inination, in an aqueous solution having a pH in excess of about 10.

The polyalkylene oxide compound which can be used in this invention is a compound having therein at least a partial structure of or units of a polyalkylene oxide which serves for increasing the infectious developing effect with the use of a silver halide photographic emulsion, such as those described, for example, in U.S. Pat. Nos. 2,400,532; 3,294,537; 3,294,540; 3,516,830; 3,567,458 and 3,345,l ;(.the latter three corresponding to French Pat. Nos. 1,491,805; 1,596,673; Japanese Pat. Publication No. 23466/ 1965 respectively),

etc. g k

Examples of suitable polyalkylene oxide compounds include an addition polymer of ethylene oxide, of propylene oxide and like alkylene oxides with a compound such as water, aliphatic alcohols, aromatic alcohols, glycols, aliphatic acids, organic amines and a dehydration compound of hexitol, a condensate of a polyalkylene oxide with one of the above group of the compounds, or an inter-block copolymer of various different alkylene oxides 6 ethylene oxideand propylene oxide). 1 f

The polyalkylene oxide compounds used in this invention has a molecular weight ranging from about 500 to 25,000, preferably'from 1,000 to 20,000, and includes, for example, the following compounds:

(wherein a, b and c are integers with b being an integer of 14 to 55 and with a+c being an integer of 4 to 2l0) A number of various commercial products satisfy the above requirements. withfa variety of values for a, b, and c and with a'v'ariety of molecular weights. These products are presently available under the trade names of Pluronic L-44, L'-6l, L -62, le -64, L-68, L-8l, P-65,

P-75 and F-88 (produced by the Wyandotte Chemical Co., respectively). For instance, L-68 has a molecular weight of 8750 with b=32, and o+c=159; P-75 has a molecular weight of 4100, with b=37, and a+c=5l; F-88 has a molecular weight of 1,1250, with b=4l and C(CH CH OLJ-I (where l+n +n is about 20) (CH,CH O),H h. CHHNCON (where p+q=40) cH,ci-i,o),ri

The silver halide emulsion used in this invention contains particles of silver chloride, silver bromide, silver iodide or mixtures, thereof and preferably consists of at least 40 mol of silver chloride and less than 5 mol of silver iodide or silver bromide. The silver halide particles used in this invention can have a uniformly distributed halogen composition inside the particles or the particle surface can have a different composition from that of the interior. The technique of the present invention can be applied not only to conventionally employed surface sensitive type negative emulsions but also to internal latent image type emulsions, direct positive type emulsions having a chemically fogged surface, and to other emulsions such as those prepared in accordance with the processes describedffor instance, in U.S. Pat. Nos. 2,592,250; 2,996,382; 3,607,278 and 3,367,778; etc.

If the average diameter of the silver halide particle is higher than 0.8 microns, the granularity of the image obtained after infectious development will become much coarser than that obtained after ordinary noninfectious type developing.

The average diameter of the silver halide particle is determined according to conventional methods.

In greater detail, these methods of particle size determination are described in Triuelli and Smith, Photographic Journal, Vol.79, pages 330-380(1939); Trivelli, Righter and Sheppard, Photographic Journal, Vol.62, Pages 407-410(1922); P. F. Utt and K. F. Leverington, The Determination of Silver Halide Crystal Distribution in Photographic Emulsion with the Zeis- Endter Particle Size Analyser, 1966 Particle Size Analysis Conference Report, pages 45-55, (published by Soc. Anal. Chem.) etc.

The photographic emulsion used in this invention can be sensitized using conventional techniques now wellknown in the art, such as those described in C. E. K.

ions (e.g., gold compounds, platinum compo'undsfet c 1 as disclosed in U.S. Pat. Nos. 2,540,085; 2,597,856;-'

2,597,915; 2,399,083, etc.), other metal ions other than silver such as metal ions of the Group VIII metals of the Periodic Table and Group 11 metal ions.

Typical examples of chemical sensitizers include thiourea, sodium thiosulfate, cystine and the like sulfur'containing sensitizers; potassium chloroaurate, aurous thiosulfate, potassium chloropalladate, and the like noble metal sensitizers; tin chloride, phenyl hydrazine, reductone and the like reducing sensitizers, etc.

Other sensitizers such as polyoxyethylene compounds (as disclosed in U.S. Pat. No. 2,716,062), polyoxypropylene compounds having an oxonium or ammonium group (as disclosed in U.S. Pat. Nos. 2,271,623; 2,288,226; and 2,334,864) can also be included.

In addition, high contrast (high gradation), stabilization, fog inhibition or supersensitization, etc. can be applied if desired.

Suitable examples thereof are antifoggants such as nitrobenzazoles, e.g., nitrobenzimidazole as disclosed in British Pat. No. 403,789, platinate salts, e.g., ammonium chloroplatinate, as disclosed in U.S. Pat. Nos. 2,566,263; and 2,566,245, etc., stabilizers such as 4-hydroxy-6-methyl-l 3,3a,7-tetrazaindene, thiazolium salts as disclosed in U.S. Pat. Nos. 2,131,038 and 2,694,716, azaindenes, e.g., 4-hydroxy- 6-methyl-l,3,3a,7-tetrazaindene as disclosed in U.S. Pat. Nos. 2,886,437 and 2,444,605, urazoles as disclosed in U.S. Pat. No. 3,287,135, sulfocatechols as disclosed in U.S. Pat. No. 3,236,652, oximes, mercaptotetrazoles as disclosed in U.S. Pat. Nos. 2,403,927, 3,266,897, and 3,397,987, nitrons, polyvalent metal salts as disclosed in U.S. Pat. No. 2,839,405, thiuronium salts as disclosed in U.S. Pat. 3,220,839, and salts of metals such as palladium, platinum and gold as disclosed in U.S. Pat. Nos. 2,566,263 and 2,597,915.

The photographic emulsion which can be used in this invention can contain as its protective colloid gelatin and acylated gelatin derivatives such as phthalated or malonated gelatin, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose; hydrophilic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polystyrene sulfonic acid, etc.; dimension stabilizing plasticizers, polymer latices such polymethyl methacrylate, polybutyl methacrylate, and matting agents such as silicon dioxide, etc.

The photographic emulsion which can be used in this invention can further contain developing accelerators such as onium compound, hydroquinone derivatives, 3-pyrazolidone derivatives and cationic surface active agents; stabilizers which are used in conventional photosensitive materials such as 4-hydroxy-l ,3,3a,7- tetrazaindene derivatives; fog inhibitors such as mercaptotetrazol and lipoic acid; hardeners including inorganic compounds and organic compounds such as formaldehyde, other aldehydes, chromalum, mucochloric acid, sodium-l-hydroxy-3,5-dichlorotriazine, glyoxal, dichloroacrolein, aziridine etc., surface active agents such as saponin, sodium alkyl benzenesulfonates, anionic surface active agents such as those described in U.S. Pat. No. 3,415,649; anionic, nonionic or amphoteric surface active agents conventionally used as coating aids such as the alkylarylsulfonates as disclosed in U.S. Pat. No. 2,600,831, amphoteric compounds as disclosed in US. Pat. No. 3,133,816; irradiation inhibiting dyes such as the merocyanine dyes, oxonol dyes, styryl dyes, naphthoquinone dyes, etc.

The layer of the photographic emulsion used in this invention can be provided with either on its upper or lower side at least one layer of a colloid which has been dyed to prevent halation or to exert a filtering activity.

The silver halide photographic emulsion can be spectrally sensitized using various methine dyes as disclosed in C. E. K. Mees The Theory ofthe Photographic Process Revised Ed. MacMillan; Frances M. Hamer The Cyanine Dyes And Related Compounds, lnterscience Publishers, e.g,, cyanine dyes, merocyanine dyes, hemicyanine dyes, complex merocyanine dyes, styryl dyes, neutrocyanine dyes, etc.

The use of sensitizing dyes represented by the following general formulae ([1) or (III) are especially desirable;

GENERAL FORMULA lI wherein Z, represents a group of atoms necessary for forming a heterocyclic ring such as a tetrazole ring, a pyrrolidine ring, a pyridine ring, a thiazole ring, a thiazoline ring, a selenazole ring, a selenazoline ring, an oxazole ring, an oxazoline ring, an imidazole ring, an imidazoline ring and an indolenine ring; L, and L each represents a methine chain, for example, a methine chain, a methyl methine chain, an ethyl methine chain, a phenyl methine chain and 2-hydroxyethyl methine chain etc.; Y, represents an oxygen atom, a sulfur atom or a =NR group in which R is an aliphatic group including a saturated aliphatic group and an unsaturated aliphatic group (e.g., an unsubstituted alkyl group and a substituted alkyl group wherein the alkyl moiety preferably has up to carbon atoms) such as an alkyl group (e.g., methyl, ethyl and propyl groups), a cyanoalkyl group (e.g., cyanoethyl) an allyl group (e.g., vinyl methyl), a carboxyalkyl group such as a carboxymethyl group and a carboxyethyl group, an aminoalkyl group such as a dimethylaminoethyl group, an aralkyl group such as p-carboxyphenylmethyl group, a hydroxyalkyl group such as a hydroxyethyl group, an aryl group such as a phenyl group, a p-sulfophenyl group, etc.; n is an integer ofO or 1; R and R are each an aliphatic group including a saturated aliphatic group and an unsaturated aliphatic group (e.g., an unsubstituted alkyl group and a substituted alkyl group wherein the alkyl moiety preferably has up to 5 carbon atoms), e.g., an alkyl group such as a methyl and ethyl group, a carboxyalkyl group (e.g., a carboxymethyl and carboxybutyl group), a sulfoalkyl group (e.g., sulfopropyl), an allyl group (e.g., vinylmethyl), an aminoalkyl group such as a morpholinoethyl group, an acetoxyalkyl group such as an acetoxypropyl group, an aralkyl group such as a benzyl group, an aryl group such as a phenyl, pcarboxyphenyl and tolyl group.

GENERAL FORMULA [ll wherein A is a hydrogen atom or a lower alkyl group containing not more than 3 carbon atoms; Z and 2,, each represents a group of atoms necessary for forming a benzene type or a naphthalene type aromatic ring; Y and Y are each an oxygen atom, a sulfur atom, a selenium atom, a =NR group, in which R is an aliphatic group including a saturated aliphatic group and an unsaturated aliphatic group (e.g., an unsubstituted alkyl group and a substituted alkyl group wherein the alkyl moiety preferably has up to 5 carbon atoms) an such as an alkyl group, e.g., a methyl, ethyl, isopropyl group etc., an allyl group (e.g., vinylmethyl), an acetoxyalkyl group (e.g., acetoxyethyl), a cyanoalkyl group such as cyanoethyl group, or

group, in which R, and R,, are each an alkyl group such as methyl or ethyl. The above aromatic ring formed by Z, and Z can be further substituted with an aryl group (e.g., phenyl, etc.), a halogen atom (e.g., chlorine, bromine, etc.), an alkyl group (e.g., methyl, ethyl, etc.), an alkoxycarbonyl group (e.g., methoxy carbonyl, ethoxy carbonyl), an alkoxy group (e.g., methoxy, ethoxy, propoxy, etc.), a trifluoromethyl group, an alkylsulfonyl group (e.g., methyl sulfonyl ethylsulfonyl, etc.). Eventually, the heterocyclic nuclei formed may include, for example, heterocyclic nuclei such as S-phenyl-benzoxazole, S-chlorobenzoxazole, 5- methylbenzoxazole, 5-methoxycarbonylbenzoxazole, 5-chlorobenzothiazole, S-methoxybenzothiazole, 5- chloro-6-methylbenzothiazole, B-naphthothiazole, B,B'-naphthothiazole, S-methylbenzoselenazole, benzoselenazole, 5,6-dichlorobenzimidazole, S-trifluoromethylbenzimidazole, 5'chloro-6-methylsulfonylbenzimidazole, S-methoxycarbonylbenzimidazole, naphthoimidazol-1,l -dimethylindolenine, etc.

R and R,, each represents an alkyl group (e.g., an ethyl group, a propyl group etc.), a substituted alkyl group (e.g., a propenyl group, a hydroxyalkyl group such as a hydroxyethyl group, an amidoalkyl group such as an amidoethyl group, an aralkyl group such as a p-carboxyphenylmethyl group, a carboxyalkyl group such as a carboxymethyl, carboxy ethyl and carboxybutyl group, a sulfo group-containing alkyl group such as sulfopropyl group, a 3-sulfobutyl group, a 2-[2-(3- sulfopropoxy)-ethoxyethyl group, etc. In addition to the above, those substituents described in E. J. Poppe, Zeitschrift fli'r Wissenschaftliche Photographie Vol. 63, pages l49l58 (1969) are also included. X represents an organic or inorganic anion generally used in a cya nine type dye such as a bromide ion, an iodide ion, a p-toluenesulfonic acid ion, a perchloric acid ion, etc. p

is l or 2, but when p is l, the compound forms an intramolecular salt.

(ll-f) The methine dyes represented by the general formula (ll) or (III) can be used alone or as a combination of The dyes which can be used can be exemplified by the following compounds, the listing of which is not to be interpreted as limiting the scope of the invention. General Formula II compounds:

CH, kCH-CH N CH H (ll-g) C 2 CH2 (ll-a) Art coon

c=s N cm, l N

m N \C/ m a Q 0 H m 4 o m C 5 w H H O\ N C i t c m t. 1 H O N w x w u w u m x 5 H M Q c N/ u mp so ua (ll-b) (ll-c) (ll-d) (ll-j) (ll-e) Examples of other compounds The polyalkylene oxide compound which can be used in this invention is added in an amount sufficient to promote infectious development desirably in an amount of from 0.01 to 1 gram per mol of silver halide. The organic compound used as one indispensable element of this invention is preferably added in an amount of from mole to 10 mole per mol of silver halide. The sensitizing dye which can be used in this invention is incorporated in a ssnsitizing amount, preferably in an amount of from 10' to 10' mol per mol of silver halide, which is sufficient to improve the sensitivity by usual sensitometry.

These additive compounds are added as solutions using solvents such as water or a suitable watermiscible solvent not adversely affecting the photographic properties of the silver halide emulsion such as alcohol (e.g., methanol, ethanol, methylcellusolve etc.), ketones (e.g., acetone, etc.).

The compound represented by the general formual (l) is preferably added as a neutral or acidic aqueous solution thereof.

These additive compounds can be incorporated using the techniques described in Japanese patent application No. 8231/1970, corresponding to US. patent application Ser. No. 111,501, filed Feb. 1, 1971 Japanese patent publication Nos. 27555/1969, 23389/1969, 22948/1969 corresponding to US. Pat. Nos. 3,574,630; 3,585,195; 3,482,981 and 3,469,987 etc.

The finished emulsion is preferably kept at the pH below 6.8, especially below 6.5.

These additive compounds can be added directly to the emulsion itself, or added to at least one of the layers adjacent to the silver halide emulsion layer (such as a protective layer or an intermediate layer, an antihalation layer or other silver halide emulsion layers) through which the compounds eventually migrate and penetrate into the main silver halide emulsion layer.

The finished emulsion of the present invention can be applied to a suitable support material such as a polyethylene terephthalate film, a polystyrene film, a cellulose acetate film, a cellulose acetate butylate film, other plastic films, glass plates, etc.

The silver halide photosensitive material obtained in accordance with the present invention can be processed or treated in any conventional manner known in the art, for instance, in vat developing, automatic developing systems using rollers, belts and like mechanical transferring devices, or any other processes generally known in the art.

The development is carried out, for instance, using an infectious developer which is fundamentally consists of dihydroxybenzene (main developing agent), inorganic or organic bases, a minor amount of sulfite salts, and buffers containing sulfuric acid and a minor amount of sulfite salts.

The dihydroxybenzenes used as the main developing agent can suitably be selected from compounds wellknown per se in photographic chemistry, and include, for example, hydroquinone, chlorohydroquinone,

The bromide ion and the iodide ion contents were 17 mol and 0.2 mol respectively, and the amount of silver per kg of the emulsion was about 1.3 mol The silver halide particles had an average diameter of bromohydroquinone, isopropylhydroquinone, methylabout 05,, hydroquihohei 2,3'diehlol'ohydroquihohe, The emulsion (2.5Kg) was weighed into a pot and the thylhydroquihohei vessel was heated to about 45C to melt the contents.

These compounds can be e e'ther Smgly or as The contents were then spectrally sensitized by adding tures thereof as g gap g P ai of 1O 100cc of 2 x 10- mol solution of the sensitizing dye amount used can e a e to t e s1ver a1 e emu (we) in methanoL s1on.

The sulfite ion buffer is used in an effective amount 353332;:2 2:: Z; so as keep e concentration of the sulfifie ions as low a stabilizer to the resulting solution. Thereafter the nec- 21? 23 5313 111 5;: 332 131213? i'i iiil ilidlliii u l'fii; i additives were added acwdmg o acetone-alkali bisulfite adduct, and carbonyl bisulfuric as Show]? Table 1 under Surfing at about 45 l The add1t1on of a compound selected from polyalacid am1ne condensate such as sodlum b1s-(2-hydroxkylene oxide compounds eth l)aminomethane sulfonate.

y In order to render the developer liquid alkaline, pref- 2 The addmon of a compound Selected from the erably to a pH above 9.5, certain alkaline compounds group of compounds represented by gemal including sodium carbonate, sodium bicarbonate, pomula I tassium carbonate, potassium bicarbonate, sodium hy- To each emulslon'thus obtained were added 50 cc of droxide, potassium hydroxide, organic bases Such as a 1% aqueous solut1on of sod1um dodecylbenzene sul- 2-aminomethanol, 2,2-iminodiethanol, triethanolfonate and 50cc of a 2% Solution of y yi amine, 2 ethylamin0ethano|, flu are added to the 25 dichloro-S-triazine sodium salt, and the resulting emulveloper. These alkaline compounds can be added eision was applied to a glass Plate and dried to form 3 mar alone or in combination coating having dried film thickness of 1011..

The developer liquid can be further contain at least After cutting into P i the photosensitive material one of the following various additives well-known to so obtained was Wedge-exposed using a sehsitometel' those skilled in the art, such as, for example, benzothihaving a color temperature of 54000K- The thus azole, 1-phenyl-5-mercaptotetrazole and like organic Posed Strip was developed using a conventional fog inhibitors, polyalkylene oxides, amine compounds, type developer having the following composition at onium compounds and organic solvent such as triefor 3 and 4 minutes respectivelythyleneglycol monoalkylether, etc.

The developer liquid can be prepared in the form of Composition of Dcvelopcrl a powder of the developer components which has been water 500 cc widely used up to now, or in the form of a liquid con- Hydmquinone 15 g taining the component which has been recently used gs g z Fmmaldehyde with 50mm 50 g with increasing interest to improve working efficiency 40 potassium Carbonate 35 g and along with the increasingly widespread use of auto- Triefhanolamine Ce matic developing apparatus. :15??? g The techniques in accordance with this invention can Potassium Bromide be applied in combination with other already known water) make 1 techniques such as those described in U.S. Pat. Nos. 3,252,101; 3,345,175; 3,220,844; 3,294,540; Composition of Fixing Liquid 3,447,459; 3,433,639; 3,294,537; 3,516,830; water 600 cc 3,518,085; 3,615,524; 3,567,458; 3,625,689; Sodium Thiosulfate 360 g 3,600,174; 3,142,568; 3,325,286; and 3,346,368; Britg 'ygl kig sf Sulfite 2 ish Pat. Nos. 1,098,748; and 1,163,724; and Ger,an 5o Glacial Acetic Acid 13.5 g .Pat. Nos. 1,141,531; and 2,010,992; etc. gggg gtfjf g The present invention is illustrated in greater detail water to make 1 m by the following examples. Unless otherwise indicated, all parts and percents are by weight. The strips so processed was subject to densitometry EXAMPLE 1 so as to obtain characteristic curves, and the sensitivit1es thereof were calculated relatively taking the inertla A chemically ripened silver isdochlorobromide emulpoint of the gradient scale obtained after infectious desion was prepared according to a conventional method. velopment as a standard.

Table 1 No. Polyalkyleneoxide Compound of General Result (C0nc.=0.5%) cc Formula (I) (Conc.=1 10'mol)cc 1 2 (A) FIG. 1 Curve 1 3 do. 100 (l-a) 40 do. Curve 2 4 do. 100 (l-f) do. Curve 3 5 (A) 100 (l-d) 40 FIG. 2, Curve 4 6 (A) 100 (a) 40 do. Curve 5 In the above Table 1; I A. was a polyethyleneoxide compound having aparoximately 50 ethyleneoxide units in to each oleyl- Jhenoxy group.

Quantum Ch; HO D N(CMMHCI a. A compound for comparison CH N t D HO- HCl EXAMPLE 2 The same original emulsion as was employed in Example l was weighed into a pot each in a 100g portion, heated at 45C to melt it, then spectrally sensitized by adding 100cc ofa 1 X 10 mol solution of the sensitizing dye (ll-j) in methanol.

Using the procedure of Example 1, a polyalkyleneoxide compound, a compound represented by the general formula (1) and 6cc of 2% solution of mucochloric acid to give finished solution were added and the emulsion was thereafter applied to a polyethylene terephthalate film and dried to form a layer having a dried film thickness of about 6p" Composition of Developer Liquid 1! 500 cc 15g Water Hydroquinone Adduct of Formaldehyde with Sodium Bisulfite Sodium Carbonate Sodium Sulfite Boric Acid Potassium Bromide Water to make g g 25 g 5.0 g 2.0 g

1 liter Table 2 Polyalkyleneoxide (Conc. cc

General Formula (1) Relative Sensitivity Developing Time 2 min. 3 min. 4 min.

Compound of Points Period of Development Time 2 min. 3 min.

(Conc. cc

Quality of Cross Line 4 min.

(B) 0.5% 5cc 2% Sec C B B (l-a) 0.5?! 1.5cc

(1-3)0.57r 1.5cc 150 88 45 143 (1-a) 0.5% 1.5cc

Runs No. 1, 2 and 6 were carried out for the purposes of comparison. The results of Run No.5 clearly demon- 65 strate the advantageous feature of the present invention in comparison with Run No. 6.

No infectious development took place.

In Table 2:

B. A polyethylene oxide compound having approximately 30 ethylene oxide units to every oleylphenoxy group C. Pluronic L-35, manufactured by the Wyandotte Chemical Co.

D. Polyoxyethylene sorbitan monooleate (n=40) E. Polyoxyethylene laurate (n=40) The cross line point quality was classified into 3 grades in the order of the sharpness of the cross line edge, i.e., A B C, by comparing with that of the standard sample (strips used for development for 3 minutes methods known and employed ordinarily by those skilled in the art.

EXAMPLE 4 of Run No. 7). (Refer to the description of Japanese 5 h l d oxlclatlon Potential M) ed in this inpatent application Ser. No. 3037/1962 corresponding vgmlon etelrmmed acCOrdmg t the method as to US. patent application Ser. No. 319815 filed Dec. S own prev'ofls v 29 1972) The potential current curve by taking hydroquinone I as the standard material is shown in FIG. 3.

EXAMPLE 3 10 The values of the E of the compounds represented A chemically ripened silver iodochlorobromide by the general formula are g n as follows: emulsion was prepared according to conventional method. The emulsion had a bromide ion content of 17 (La) minim" (mv) mol and an iodine ion content of 1 mol%. The emul- (Ld) sion contained 80cc of a 4 X 10 mol solution of dye 5 3-2 1(5)? II-a in methanol and 50 cc of a 1 X mol solution (H) of dye 11-1 in methanol in each kg. to effect spectral sen- 1) 1 sitization. To the thus spectrally sensitized emulsion gydmquinone 328 were added 500cc of a 1% solution of 4hydroxy-6- (standard) methyl-I,3,3a,7-tetrazaindene and a predetermined 2O amount ofa polyoxyethylene compound (A), then 100 In FIG. 3, the middle points of the curves between cc of a 2% solution of 6-hydroxy-2,4-dichloro-S- each of the upper limit and the lower limit in the orditriazine sodium salt was added to provide the finished nate direction ordinate which indicates current values emulsion. are connected to give three extended line segments.

On one hand, a collo'idal composition to be used for The points at which the line segments cross are indimaking a protective layer was prepared, and thereafter cated as points a and b, respectively. The middle point the compound represented by the general formula (I) p of the line segment formed between crosspoint a and was admixed thereto. 4 crosspoint b is determined. The oxidation potential value (E of the present invention is then obtained as a voltage value corresponding to point p. While the invention has been described in detail and Composition of COllOICl for Protective Layer: I

with reference to specific embodiments thereof, 1t Wlll Gelatin 50 g be apparent to one skilled in the art that various Water 1000 cc 1 Silicon Dioxide 02 g changes and modifications can be made therein with- Sodium 4 5 14 out departing from the spirit and scope thereof. tetradecane-l-sulfonate (2%) cc What is l i d i 1. In a lithographic silver halide photographic emul- "-sion comprising at least 40 mol of silver chloride and A lij f li k l l g fizi z film g flfisfly containing silver halide particles with the average partig j g 3 l r r f m 3 40 cle diameter of not more than 0.8'micron, the improvef "g 3 g t l a d ment which comprises said silver halide photographic f er come t 6 Protective ayer m a He emulsion containing the combination'of the following fllm thickness of about In. 7 compounds: 1

In a mann er similar to Example 2, the resulting phoa polyalkylene oxide compound, and tosensitlve film was exposed under a cross line screen an Organic compound of the general formula (I) and developed with the use of a roller type automatic R developer and the developer liquid (I) at 27C for 75, XOAN 105 and 135 seconds, respectively. R1

' Table 3 Polyalkylene Compound of General Formula (1) Relative Sensitivity Quality* of CrossLine Point oxide Added cc Added to Emulsion Added to Protective (Conc. cc Colloid Layer sec. sec. sec. 75 sec. 105 sec. 135 sec.

(conc. cc

(A) 35 36 100 158 C B B (I-a) 0.5% 20 128 181 226 B A B (H) 0.5% 8 153 193 230 A B B (H) 0.5% 15 100 149 190 B A A (A) 35 40 100 C B B (I-a) 0.5% 30 142 I83 207 B A B (I-a) 0.5% 50 184 212 230 A B c Grades as previously described in Table 2 wherein A represents a bivalent aromatic or heterocy- 65 clic group,'R and R each represents a group which is necessary to form a tertiary amino group with the nitrogen atom, and R and R can combine together to form a ring; X represents either hydrogen, or a group capable of being dissociated therefrom with an inorganic or organic base, or a precursor of said organic compound having the general formula (I), said compound of the general formula (I) having an oxidation potential ranging from O millivolt to -200 millivolt.

2. The photographic emulsion of claim 1, in which said organic compound has the general formula (I) XOAN R2 wherein A represents a bivalent aromatic or heterocylic group, R, and R each represents a group which is necessary to form a tertiary amino group with the nitrogen atom, and R, and R can combine together to form a ring; X represents either hydrogen, or a group capable of being dissociated therefrom with an inorganic or organic base, or a precursor of said organic compound having the general formula (I), said compound of the general formula (I) having an oxidation potential ranging from 0 millivolt to 2OO millivolt.

3. The photographic emulsion of claim 1, in which said organic compound has the following general formula (Ia) wherein B represents a bivalent benzene type aromatic ring group, and X, R, and R each is as defined in claim 1.

4. The photographic emulsion of claim 1, wherein A is a unsubstituted or substituted benzene group, naphthalene group, pyrimidine group, or triazine group, said substituents being alkyl, alkoxy, hydroxy, halogen, alkoxycarbonyl, quaternary aminoalkyl, aralkyl or aryl groups; R, and R each is an alkyl group, an alkenyl group, an aralkyl group or an aryl group or R, and R can combine together to form a saturated or unsaturated ring; X represents a hydrogen atom, an acyl group, or an acyloxy group.

5. The photographic emulsion of claim 1, wherein said polyalkylene oxide compound has a molecular weight ranging from about 500 to 25,000.

6. The photographic emulsion of claim 5, wherein said polyalkylene oxide compound is CH-CHxHITZ CH wherein a, b and c are integers with b being an integer of 14 to 55 and with a+c being an integer of 4 to 210;

d. Ho-cH cHp-ecmcH om-cH cH oH;

wherein 1 +m+n is about 20;

Ho N .HCl

CH HO- N/ .HCl

HD- -N(CH,),.HCI

CH, HO- N(C,H,),.HCI

CH HONmC HQ HCl CH, HOQNWC HCI HO DMQHQTHCI co o @mcnnmmso,

H GINC HQ HCI SO H OCH

HOGLHCQHSLHO or CH CH 8. The photographic emulsion of claim 1, wherein said emulsion contains at least one of a sensitizing dye of the general formula ([1) wherein Z represents a group of atoms necessary for forming a heterocyclic ring; L and L each represents a methine chain; Y represents an oxygen atom, a sulfur atom or a =N-R group in which R is an aliphatic group or an aryl group; n is an integer ofO or l; R, and R are each an aliphatic group or an aryl group; and a compound of the general formula (Ill) (Ill) wherein A is a hydrogen atom or a lower alkyl group containing not more than 3 carbon atoms; Z and Z each represents a group of atoms necessary for forming a benzene or a naphthalene ring; Y and Y are each an oxygen atom, a sulfur atom, a selenium atom, a =NR group, in which R is an aliphatic group, or

group, in which R and R are each an alkyl group; R and R each represents an aliphatic group; X is an anion; and p is 1 or 2, p being 1 when the compound forms an intramolecular salt.

9. The photographic emulsion of claim 8, wherein said Z is a tetrazole ring, a pyrrolidine ring, a pyridine ring, a thiazole ring, a thiazoline ring, a selenazole ring, a selenazoline ring, an oxazole ring, an oxazoline ring, an imidazole ring, an imidazoline ring or an indolenine ring and wherein said heterocyclic ring formed Z and Z each is S-phenyl-benzoxazole, 5 -chlorobenzoxazole, S-methylbenzoxazole, 5-methoxycarbonylbenzoxazole, S-chlorobenzothiazole, S-methoxybenzothiazole, 5- chloro-6-methylbenzothiazole, B-naphthothiazole, B,B-naphthothiazole, S-methylbenzoselenazole, ben zoselenazole, 5,6-dichlorobenzimidazole, 5-trifluoromethylbenzimidazole, 5-chloro-6-methylsulfonylbenzimidazole, S-methoxycarbonylbenzimidazole, or naphthoimidazol-l ,1 dimethylindolenine.

10. The photographic emulsion of claim 8, wherein R and R each is an alkyl group, a carboxyalkyl group, a sulfoalkyl group, an allyl group, an aminoalkyl group,

an acetoxyalkyl group, an aralkyl group or an aryl group and wherein R-, and R each is an alkyl group, an alkenyl group, a hydroxyalkyl group, an amidoalkyl group, an aralkyl group, a carboxyalkyl group or a sulfo alkyl group.

11. The photographic emulsion of claim 10, wherein L and L each is a methine chain, a methyl methine chain, an ethyl methine chain, a phenyl methine chain and a 2-hydroxyethyl methin chain R is' an alkyl group, a cyanoalkyl group, an allyl group, carboxyalkyl group, an aminoalkyl group, an aralkyl group a hydroxyalkyl group or an aryl group; R is an alkyl group, an ally] group, an acetoxyalkyl group, a cyanoalkyl group or group and R and R are each an alkyl group.

12. The photographic emulsion of claim 1, wherein said emulsion contains at least one dye selected from the group consisting of -Cntinued 2 5 o 0 \C=CHCL=CH-C/+ N/ bll cl (CH MSO N'a cHmso S iz s s N CCH CHC N n'l hso Na (CH)=SOJ =CHCH= C=CH-C @(D N/ s,

13. A silver halide photosensitive material containing as a photosensitive layer thereof the silver halide photographic emulsion as claimed in claim 1.

14. The photographic emulsion of claim 13, in which said organic compound has the following general formula (1-0) wherein B represents a bivalent benzene type aromatic ring group, and X, R and R each is as defined in claim 1.

15. The silver halide photosensitive material of claim 13, wherein A is a unsubstituted or substituted benzene group, naphthalene group, pyrimidine group, or triazine group, said substituents being alkyl, alkoxy, hydroxy, halogen, alkoxycarbonyl, quaternary aminoalkyl, aralkyl or aryl groups; R, and R each is an alkyl group, an alkenyl group, an aralkyl group or an aryl group or R and R, can combine together to form a saturated or unsaturated ring; X represents a hydrogen atom, an acyl group, or an acyloxy group.

16. The silver halide photosensitive material of claim 13, wherein said polyalkylene oxide compound has a molecular weight ranging from about 500 to 25,000.

. 17. The silver halide photosensitive material of claim 16, wherein said polyalkylene oxide compound is a. Ho-CH,CH, 0+CH,CH,0 +-C.H.,;

bv HOCH=CH O(-CH,CH,O-)- CO(CH2)-,CH=CH-C H,

c. H0+CH,CH O-) ('CHCH, O);(CH,CH O).H

wherein a, b and c are integers with b being an integer of 14 to 55 and with a+c being an integer of 4 to 2l0; d. HOCH CH=O(-CH,CH,O-) ;CH CH,Ol-l;

wherein l+m+n is about 20;

18. The silver halide photosensitive material of claim 13, wherein said organic compound of the general formula (I) is 

1. IN A LITHOGRAPHIC SILVER HALIDE PHOTOGRAPHIC EMULSION COMPRISING AT LEAST 40 MOL% OF SILVER CHLORIDE AND CONAINING SILVER HALIDE PARTICLES WITH THE AVERAGE PARTICLE DIAMETER OF NOT MORE THAN 0.8 MICRON, THE IMPROVEMENT WHICH COMPRISES SAID SILVER HALIDE PHOTOGRAPHIC EMULSION CONTANING THE COMBINATION OF THE FOLLOWING COMPOUNDS,
 1. A POLYALKYLENE COMPOUNDS.
 2. AN ORGANIC COMPOUND OF THE GENERAL FORMULA (1)
 2. an organic compound of the general formula (I)
 2. The photographic emulsion of claim 1, in which said organic compound has the general formula (I)
 3. The photographic emulsion of claim 1, in which said organic compound has the following general formula (I-a)
 4. The photographic emulsion of claim 1, wherein A is a unsubstituted or substituted benzene group, naphthalene group, pyrimidine group, or triazine group, said substituents being alkyl, alkoxy, hydroxy, halogen, alkoxycarbonyl, quaternary aminoalkyl, aralkyl or aryl groups; R1 and R2 each is an alkyl group, an alkenyl group, an aralkyl group or an aryl group or R1 and R2 can combine together to form a saturated or unsaturated ring; X represents a hydrogen atom, an acyl group, or an acyloxy group.
 5. The photographic emulsion of claim 1, wherein said polyalkylene oxide compound has a molecular weight ranging from about 500 to 25,000.
 6. The photographic emulsion of claim 5, wherein said polyalkylene oxide compound is
 7. The photographic emulsion of claim 1, wherein said organic compound of the general formula (I) is
 8. The photographic emulsion of claim 1, wherein said emulsion contains at least one of a sensitizing dye of the general formula (II)
 9. The photographic emulsion of claim 8, wherein said Z1 is a tetrazole ring, a pyrrolidine ring, a pyridine ring, a thiazole ring, a thiazoline ring, a selenazole ring, a selenazoline ring, an oxazole ring, an oxazoline ring, an imidazole ring, an imidazoline ring or an indolenine ring and wherein said heterocyclic ring formed Z2 and Z3 each is 5-phenyl-benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-methoxycarbonylbenzoxazole, 5-chlorobenzothiazole, 5-methoxybenzothiazole, 5-chloro-6-methylbenzothiazole, Beta -naphthothiazole, Beta , Beta ''-naphthothiazole, 5-methylbenzoselenazole, benzoselenazole, 5,6-dichlorobenzimidazole, 5-trifluoromethylbenzimidazole, 5-chloro-6-methylsulfonylbenzimidazole, 5-methoxycarbonylbenzimidazole, or naphthoimidazol-1,1''-dimethylindolenine.
 10. The photographic emulsion of claim 8, wherein R4 and R5 each is an alkyl group, a carboxyalkyl group, a sulfoalkyl group, an allyl group, an aminoalkyl group, an acetoxyalkyl group, an aralkyl group or an aryl group and wherein R7 and R8 each is an alkyl group, an alkenyl group, a hydroxyalkyl group, an amidoalkyl group, an aralkyl group, a carboxyalkyl group or a sulfo alkyl group.
 11. The photographic emulsion of claim 10, wherein L1 and L2 each is a methine chain, a methyl methine chain, an ethyl methine chain, a phenyl methine chain and a 2-hydroxyethyl methin chain R6 is an alkyl group, a cyanoalkyl group, an allyl group, carboxyalkyl group, an aminoalkyl group, an aralkyl group a hydroxyalkyl group or an aryl group; R9 is an alkyl group, an allyl group, an acetoxyalkyl group, a cyanoalkyl group or a
 12. The photographic emulsion of claim 1, wherein said emulsion contains at least one dye selected from the group consisting of
 13. A silver halide photosensitive material containing as a photosensitive layer thereof the silver halide photographic emulsion as claimed in claim
 1. 14. The photographic emulsion of claim 13, in which said organic compound has the following general formula (I-a)
 15. The silver halide photosensitive material of claim 13, wherein A is a unsubstituted or substituted benzene group, naphthalene group, pyrimidine group, or triazine group, said substituents being alkyl, alkoxy, hydroxy, halogen, alkoxycarbonyl, quaternary aminoalkyl, aralkyl or aryl groups; R1 and R2 each is an alkyl group, an alkenyl group, an aralkyl group or an aryl group or R1 and R2 can combine together to form a saturated or unsaturated ring; X represents a hydrogen atom, an acyl group, or an acyloxy group.
 16. The silver halide photosensitive material of claim 13, wherein said polyalkylene oxide compound has a molecular weight ranging from about 500 to 25,000.
 17. The silver halide photosensitive material of claim 16, wherein said polyalkylene oxide compound is
 18. The silver halide photosensitive material of claim 13, wherein said organic compound of the general formula (I) is
 19. The silver halide photosensitive material of claim 13, wherein said emulsion contains at least one of a sensitizing dye of the general formula (II)
 20. A phototypesetting material containing the silver halide photographic emulsion as claimed in claim
 3. 21. The phototypesetting material of claim 20 wherein R1 and R2 each is an alkyl group, an alkenyl group, an aralkyl group or an aryl group or R1 and R2 can combine together to form a saturated or unsaturated ring; X represents is a hydrogen atom, an acyl group, or an acyloxy group.
 22. The phototypesetting material of claim 20, wherein said polyalkylene oxide compound has a molecular weight ranging from about 500 to 25,000.
 23. The phototypesetting material of claim 22, wherein said polyalkylene oxide compound is
 24. The phototypesetting material of claim 23, wherein said organic compound of the general formula (I) is
 25. The phototypesetting material of claim 20, wherein said emulsion contains at least one of a sensitizing dye of the general formula (II)
 26. The emulsion of claim 1 wherein said OX-group is in the position ortho to said N-atom.
 27. The emulsion of claim 1 wherein said OX-group is in the position para to said N-atom.
 28. The emulsion of claim 1 wherein X is hydrogen.
 29. The emulsion of claim 1 wherein X is a group capable of being dissociated therefrom with an inorganic or organic base.
 30. The emulsion of claim 4 wherein A is said benzene group.
 31. The emulsion of claim 4 wherein A is said naphthalene group.
 32. The emulsion of claim 4 wherein A is said pyrimidine group.
 33. The emulsion of claim 4 wherein A is said triazene group.
 34. The silver halide photosensitive material of claim 13 wherein said OX-group is in the position ortho to said N-atom.
 35. The silver halide photosensitive material of claim 13 wherein said OX-group is in the position para to said N-atom.
 36. The silver halide photosensitive material of claim 13 wherein X is hydrogen.
 37. The silver halide photosensitive material of claim 13 wherein X is a group capable of being dissociated therefrom with an inorganic or organic base.
 38. The silver halide photosensitive material of claim 15 wherein A is said benzene group.
 39. The silver halide photosensitive material of claim 15 wherein A is said naphthalene group.
 40. The silver halide photosensitive material of claim 15 wherein A is said pyrimidine group.
 41. The silver halide photosensitive material of claim 15 wherein A is said triazene group.
 42. The phototypesetting material of claim 20 wherein said OX-group is in the position ortho to said N-atom.
 43. The phototypesetting material of claim 20 wherein said OX-group is in the position para to said N-atom.
 44. The phototypesetting material of claim 20 wherein X is hydrogen.
 45. The phototypesetting material of claim 20 wherein X is a group capable of being dissociated therefrom with an inorganic or organic base. 